We propose the Vectorial E-field Characterization Through all-Optical and self-Referenced (VECTOR) method to characterize vectorial optical arbitrary waveform with up to 100% duty cycle, which is free of ambiguity, iteration, radio-frequency or external optical reference, restriction on repetition rate, and requirement of external interferometric stabilization. The feasibility of VECTOR is experimentally verified by different waveforms created by a phase-modulated CW comb source and a built-in polarization line-by-line pulse shaper.